學生：江柏誼 指導教授：于淑君 博士

1. Thioacetalization Synthesis and Structural Characterization, of Nickel(II) Complexs Supported by Aminodipyridylphosphine Oxide Ligand.The Catalytic Application to Thioacetalization of Aldehyde 學生：江柏誼 指導教授：于淑君 博士

2. Corey-Seebach Reaction Base n=2-6 n=2-6 Seebach, D.; Jones, N. R.; Corey, E. J. J. Org. Chem. 1968, 33, 300-105.

3. Acetalization and Thioacetalization of Carbonyl Compounds

4. The Earlier Catalyst for Thioacetalization J.W. Ralls, et. al., J. Am.Chem. Soc.1949, 71, 3320-3325

5. HCl Catalyzed Thioacetalization Robert Ramage, et. al., J. Chem. Soc., Perkin Trans. 11984, 71, 1547-1553.

6. Lewis Acid CatalyzedThioacetalization • Conventional Lewis Acids BF3-Et2O、ZnCl2、AlCl3、SiCl4、LiOTf、InCl3 Nakata, T. et. al., Tetrahedron Lett. 1985, 26, 6461-6464. Evans, D. V. et. al., J. Am. Chem. Soc. 1977, 99, 5009-5017. Firouzabadi, H. et. al., Bull. Chem. Soc. Jpn.2001, 74, 2401-2406. • Transition Metal Lewis Acids TiCl4、WCl6、CoCl2、Sc(OTf)3、MoCl5、NiCl2 Kumar, V. et. al., Tetrahedron Lett. 1983, 24, 1289-1292. Firouzabadi, H. et., al. Synlett 1998, 739-741. Goswami, S. et. al., Tetrahedron Lett.2008, 49, 3092-3096. • Lanthanide Metal Lewis Acids Lu(OTf)3、 Nd(OTf)3 Kanta, D. S. J. Chem. Res. Synop. 2004,230-231. Kanta, D. S. Synth. Commun. 2004, 34, 230-231.

7. BF3-Et2O Catalyzed Thioacetalization Paulo J.S. Moran. J. Organomet. Chem. , 2000, 603, 220-224 One use only

8. MoCl5 or MoO2Cl2 Catalyzed Thioacetalization One use only S. Goswami, A. C. Maity . Tetrahedron Letters, 2008, 49, 3092–3096

9. 5 mole% CoCl2 1hr 91 % One use only CoCl2Catalyzed Thioacetalization Surya Kanta De. Tetrahedron Letters, 2004, 45, 1035–1036

10. Nickel(II) Chloride CatalyzedThioacetalization 10 mole % NiCl2 2.5 hour 96 % One use only A. T. Khan et al., Tetrahedron Lett.2003, 44, 919–922

11. Motivation 1.Traditional high valent metal halide Lewis acids are difficult to handle ex. MCln ,M=Zn、W、Co、Mo….. 2.Nickel is less expensive than other transition metal NiCl2 50g $ 29.2 WCl6 100g $ 152.5 PdCl2 25g $ 849 NIBr2 50g $ 72.2 W(CO)6 50g $ 176 3.(DME)NiBr2 as preferable precursor not (DME)NiCl2 [HO(CH2)11N(H)P(O)(2-py)2]NiBr2 &[HO(CH2)11N(H)P(O)(2-py)2]NiCl2 4.Use HO(CH2)11N(H)P(O)(2-py)2 as chelate ligand [HO(CH2)11N(H)P(O)(2-py)2]NiBr2

12. Comparison of M2+(d8 species) Square Planar vs. Tetrahedral Complexes • Ni => small Δo => tetrahedral & square planar • Pd & Pt => large Δo => square planar • Ligands => large , weak-field => tetrahedral • Ligands => small, strong-field => square planar

13. Square Planar - Tetrahedral Isomerism of Nickel Halide Complexes of Ni(PPh2R)2X2 • The tetrahedral structure is increasingly favored in the orders • PPh2R：P(C2H5)3 < P(C2H5)2C6H5 < PC2H5(C6H5)2 < P(C6H5)3 • X ： Cl < Br < I R. G. Hayter, F. S. Humiec. Inorg. Chem. 1965, 12, 1701-1706.

14. Preparation of Aminodipyridylphosphine Oxide Ligand 93 % 1 75 % 2

15. Preparation of Nickel(II) Complex Catalyst 2 3 76 % Paramagnetic

16. Chemical Shift of Paramagnetic Compounds for NMR due to the paramagnetic center presence δobserved =δdiamagnetic + δhyperfine δdiamagnetic =diamagnetic shift corresponds to the values for the free ligand. δhyperfine =δcontact + δdipolar δcontact = contact shifts are caused by spin delocalization of the unpaired electrons through chemical bonds (through bond) δdipolar= dipolar shifts, between the paramagnetic center and the nucleus of interaction (through space) Major Broad signal J. Phys. Chem. A, 2003, 107, 5821-5825

17. Square planar Tetrahedral

18. IR of [HO(CH2)11N(H)P(O)(2-py)2]NiBr2 HO(CH2)11N(H)P(O)(2-py)2 [HO(CH2)11N(H)P(O)(2-py)2]NiBr2 1569 cm-1 1428 cm-1 1593 cm-1 1430 cm-1

19. EPR of HO(CH2)11N(H)P(O)(2-py)2]NiBr2 g = 2.18 g=2

20. SUQID of HO(CH2)11N(H)P(O)(2-py)2]NiBr2 χ = m / H χm = (χ / W) × M μeff = (3k / Nβ2)1/2(χmT)1/2 = 2.828(χmT)1/2 m ：磁矩, H ：外加磁場 (10000 guess), χ：磁化率 χm：莫耳磁化率, W：樣品重量, M：樣品分子量 μeff：有效磁矩, T ： 溫度, β：波耳磁元 K ：波茲曼常數, N：6.02 x 1023 slope = 1/(χmT) = 0.936 χmT = 1/0.936 μeff = 2.828 (χmT)1/2 μeff = 2.92

21. HO(CH2)11N(H)P(O)(2-py)2]NiBr2 μeff = 2.92 Tetrahedral The Organometallic Chemistry of The Transition Metals. 2005

22. FAB-MS of HO(CH2)11N(H)P(O)(2-py)2]NiBr2 HO(CH2)11N(H)P(O)(2-py)2]NiBr+ = 528 m+/Z

23. Nickel Lewis Acids Complex CatalyzedThioacetalization = Thiol =

31. Comparison of Catalytic Activity Amoung Various Different Catalyst

32. Proposed Mechanism δ (3)

33. Recyclable Nickel(II) Complex Catalyst for Thioacetalization of Aldehyde 1H NMR  Solvent= CDCl3 (0.01478M 4-Iodoanisole)

34. NiBr2(DME) Near FutureWork for Nickel(II) Complex • Immobilization onto AuNPs surfaces Cat.

35. Conclusions 1.We have successfully synthesized an air- and water-stable and efficient catalyst { [HO(CH2)11NHPOpy2]NiBr2}. 2. We use 1H NMR、 FT-IR、EPR、SQUID and FAB-MS for structural characterization of Nickel(II) complex, we have proved the compound demonstrated that it is a paramagnetic tetrahedral compound, and we will proceed detection of Elemental Analysis (EA). 3.In Ni-catalyst series, the Nickel(II) complex only can be reused for catalytic of thioacetalization of aldehyde many times without any loss of reactivity.